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Single molecule demonstration of Debye–Stokes–Einstein breakdown in polystyrene near the glass transition temperature

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  • Nicole L. Mandel

    (Columbia University)

  • Soohyun Lee

    (Sungkyunkwan University)

  • Kimyung Kim

    (Sungkyunkwan University)

  • Keewook Paeng

    (Sungkyunkwan University)

  • Laura J. Kaufman

    (Columbia University)

Abstract

Rotational-translational decoupling, in which translational motion is apparently enhanced over rotational motion in violation of Stokes-Einstein (SE) and Debye-Stokes-Einstein (DSE) predictions, has been observed in materials near their glass transition temperatures (Tg). This has been posited to result from ensemble averaging in the context of dynamic heterogeneity. In this work, ensemble and single molecule experiments are performed in parallel on a fluorescent probe in high molecular weight polystyrene near its Tg. Ensemble results show decoupling onset at approximately 1.15Tg, increasing to over three orders of magnitude at Tg. Single molecule measurements also show a high degree of decoupling, with typical molecules at Tg showing translational diffusion coefficients nearly 400 times higher than expected from SE/DSE predictions. At the single molecule level, higher degree of breakdown is associated with particularly mobile molecules and anisotropic trajectories, providing support for anomalous diffusion as a critical driver of rotational-translational decoupling and SE/DSE breakdown.

Suggested Citation

  • Nicole L. Mandel & Soohyun Lee & Kimyung Kim & Keewook Paeng & Laura J. Kaufman, 2022. "Single molecule demonstration of Debye–Stokes–Einstein breakdown in polystyrene near the glass transition temperature," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-31318-z
    DOI: 10.1038/s41467-022-31318-z
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    References listed on IDEAS

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    1. Pablo G. Debenedetti & Frank H. Stillinger, 2001. "Supercooled liquids and the glass transition," Nature, Nature, vol. 410(6825), pages 259-267, March.
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